JP2019219648A - Positively charged toner - Google Patents

Abstract

To provide a positively charged toner that is excellent in low-temperature fixability and heat-resistant storage property, and durability and chargeability.SOLUTION: A positively charged toner includes toner particles containing a binder resin; the binder resin contains a polymer A having a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer; the first polymerizable monomer is at least one selected from the group consisting of a (meth)acrylic ester with an alkyl group having 18 to 36 carbon atoms; the content ratio of the first monomer unit in the polymer A is 5.0 to 60.0 mol%; the content ratio of the second monomer unit is 20.0 to 95.0 mol%; SPof the first monomer unit and SPof the second monomer unit satisfy 3.00≤(SP-SP)≤25.00; the work function of the toner is 5.0 to 5.4 eV.SELECTED DRAWING: None

Description

  The present invention relates to a positively chargeable toner (hereinafter, may be simply referred to as “toner”) used in an electrophotographic method, an electrostatic recording method, and a toner jet recording method.

In recent years, energy saving has been considered as a major technical issue in electrophotographic apparatuses, and significant reduction in the amount of heat applied to a fixing device is being studied. In particular, there is an increasing need for so-called “low-temperature fixability” for toner, which enables fixing with lower energy.
As a technique for enabling fixing at a low temperature, there is a method of lowering the glass transition temperature (Tg) of the binder resin in the toner. However, since lowering the Tg leads to lowering the heat-resistant storage stability of the toner, it is said that it is difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner in this method.
Therefore, a method of using a crystalline vinyl resin as a binder resin has been studied in order to achieve both low-temperature fixability and heat-resistant storage stability of the toner. An amorphous resin generally used as a binder resin for a toner does not show a clear endothermic peak in a differential scanning calorimeter (DSC) measurement, but when a crystalline resin component is contained, the An endothermic peak appears.
The crystalline vinyl resin has such a property that it hardly softens to its melting point because side chains in the molecule are regularly arranged. Further, the crystal is rapidly melted at the boundary of the melting point, and the viscosity is drastically reduced accordingly. For this reason, it has attracted attention as a material having excellent sharp melt properties and having both low-temperature fixability and heat-resistant storage stability.
In general, a crystalline vinyl resin has a side chain of a long-chain alkyl group in a main chain skeleton, and the long-chain alkyl group of the side chain crystallizes to show crystallinity as a resin.
On the other hand, a crystalline resin has an oriented structure at a molecular level, and thus tends to relatively hardly obtain an electrical resistance required for charging in an electrophotographic process.
If the desired chargeability is not obtained, "fogging" in which the toner is developed in the non-image area is likely to occur. Therefore, when the crystalline resin is contained in the toner in a certain amount or more, it is necessary to achieve both low-temperature fixability and chargeability at a high level.
Various proposals have been made on crystalline vinyl resins to improve low-temperature fixability, heat-resistant storage stability, or chargeability.

Patent Literature 1 proposes a toner that uses a crystalline vinyl resin having a crosslinked structure and has excellent low-temperature fixability.
Patent Document 2 proposes a toner using, as a binder resin of a toner core, a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and a polymerizable monomer forming an amorphous portion. Have been.

JP 2009-265644 A JP 2014-130243 A

However, the binder resin used for the toner described in Patent Document 1 is a crystalline vinyl resin obtained by copolymerizing only a polymerizable monomer having a long-chain alkyl group and a crosslinking agent, and has an elasticity near room temperature. It turned out that it is inferior in durability because it is low.
Further, there is no discussion on improving the chargeability of the toner.
On the other hand, it is stated that the binder resin used in the toner described in Patent Literature 2 achieves both low-temperature fixability and heat-resistant storage stability, and provides a toner having sufficient charging performance.
However, it has been found that the binder resin used in the toner has a high proportion of a structure derived from a polymerizable monomer having a long-chain alkyl group and has low elasticity at around room temperature, and thus has poor durability. . Further, the chargeability is a study for negatively charged toner, and there is room for improvement for positively chargeable toner.
Furthermore, no proposal has been made for a positively chargeable toner containing a crystalline vinyl resin as a main component of a binder resin to achieve both low-temperature fixability and chargeability, and improvements are required.
SUMMARY OF THE INVENTION The present invention provides a positively chargeable toner having excellent low-temperature fixability, heat-resistant storage stability, durability and chargeability.

The present invention
A positively chargeable toner having toner particles containing a binder resin,
The binder resin is
A first monomer unit derived from a first polymerizable monomer, and
Containing a polymer A having a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol%, based on the total number of moles of all monomer units in the polymer A;
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol%, based on the total number of moles of all monomer units in the polymer A;
When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfies (1),
The toner has a work function of 5.0 eV to 5.4 eV, and is a positively chargeable toner.
3.00 ≦ (SP ₂₁ −SP ₁₁ ) ≦ 25.00 (1)

Also, the present invention
A positively chargeable toner having toner particles containing a binder resin,
The binder resin is
A first polymerizable monomer, and
Containing polymer A which is a polymer of a composition containing a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Satisfies the following expression (2),
The toner has a work function of 5.0 eV to 5.4 eV, and is a positively chargeable toner.
0.60 ≦ (SP ₂₂ −SP ₁₂ ) ≦ 15.00 (2)

  According to the present invention, it is possible to provide a positively chargeable toner having excellent low-temperature fixability and heat-resistant storage property, and excellent durability and chargeability.

Schematic diagram of cell for work function powder measurement Example of work function measurement curve

［式（Ａ）中、Ｒ_１は、水素原子、又はアルキル基（好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基）を表し、Ｒ_２は、任意の置換基を表す。］
結晶性樹脂とは、示差走査熱量計（ＤＳＣ）測定において明確な吸熱ピークを示す樹脂を指す。 In the present invention, description of “XX or more and YY or less” or “XX to YY” representing a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
In the present invention, the (meth) acrylate means an acrylate and / or a methacrylate.
In the present invention, the “monomer unit” is defined as one unit of one section of a carbon-carbon bond in a main chain obtained by polymerizing a vinyl monomer in a polymer.
The vinyl monomer can be represented by the following formula (A).

[In the formula (A), R ₁ represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R ₂ represents an arbitrary substituent. . ]
A crystalline resin refers to a resin that shows a distinct endothermic peak in a differential scanning calorimeter (DSC) measurement.

Usually, a crystalline vinyl resin has a side chain of a long-chain alkyl group in the main chain skeleton, and the long-chain alkyl group of the side chain crystallizes to show crystallinity as a resin.
Therefore, when a crystalline vinyl resin having a long-chain alkyl group is used, the higher the content of the long-chain alkyl group, the higher the crystallinity, the higher the melting point, the sharper the meltability, and the lower-temperature fixing. Excellent in nature.
However, when the content ratio of the long-chain alkyl group increases, the elasticity of the crystalline vinyl resin decreases at around room temperature. As a result, the toner becomes brittle, and the durability decreases.
On the other hand, in order to improve the decrease in durability, a polymerizable monomer having a long-chain alkyl group is copolymerized with another polymerizable monomer, and the content of the long-chain alkyl group is kept at a certain level or more. When it is lowered to a lower value, the crystallinity is extremely reduced and the melting point is lowered. As a result, the heat-resistant storage stability decreases, the sharp-melt property decreases, and the low-temperature fixability also decreases.

In addition, since crystalline resins have an oriented structure at the molecular level, the electrical resistance required for charging in an electrophotographic process tends to be relatively difficult to obtain, and both low-temperature fixability and chargeability have been large. It was an issue.
In particular, in the case of a positively chargeable toner using a binder resin containing a crystalline vinyl resin as a main component, no study has been made on the chargeability, and improvement is required.

  The present inventors have solved these problems by forming a polymer used in a binder resin, the type and content of a monomer unit having a long-chain alkyl group, and the type and content of other monomer units. , And the SP value difference between these monomer units was examined. further. The present inventors have found that the present invention has studied the control of the work function of the entire toner within a specific range.

The present invention
A positively chargeable toner having toner particles containing a binder resin,
The binder resin is
A first monomer unit derived from a first polymerizable monomer, and
Containing a polymer A having a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol%, based on the total number of moles of all monomer units in the polymer A;
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol%, based on the total number of moles of all monomer units in the polymer A;
When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfies (1),
The present invention relates to a positively chargeable toner, wherein the work function of the toner is from 5.0 eV to 5.4 eV.
3.00 ≦ (SP ₂₁ −SP ₁₁ ) ≦ 25.00 (1)

Also, the present invention
A positively chargeable toner having toner particles containing a binder resin,
The binder resin is
A first polymerizable monomer, and
Containing polymer A which is a polymer of a composition containing a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Satisfies the following expression (2),
The present invention relates to a positively chargeable toner, wherein the work function of the toner is from 5.0 eV to 5.4 eV.
0.60 ≦ (SP ₂₂ −SP ₁₂ ) ≦ 15.00 (2)

  Here, the SP value is an abbreviation of a solubility parameter, and is a value serving as an index of solubility. The calculation method will be described later.

The binder resin has a first monomer unit derived from a first polymerizable monomer, and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Of polymer A having the following monomer unit.
The binder resin is a polymer A, which is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. It contains.

The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylates having an alkyl group having 18 to 36 carbon atoms. By having the first monomer unit, the polymer A becomes a resin having crystallinity.
When the number of carbon atoms is in the above range, the melting point of the polymer A tends to be 50 ° C. or more and 80 ° C. or less, and good low-temperature fixability and heat-resistant storage stability can be obtained.

When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfies (1).
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Satisfies the following expression (2). 3.00 ≦ (SP ₂₁ −SP ₁₁ ) ≦ 25.00 (1)
0.60 ≦ (SP ₂₂ −SP ₁₂ ) ≦ 15.00 (2)
The value of the _(SP 21 _{-SP 11)} is, 4.00 ^{(J /} cm 3) is preferably from ^{0.5 ~20.00 (J / cm 3)} 0.5, 5.00 (J / cm ³ ) More preferably, it is ^{0.5 to} 15.00 (J / cm ³ ) ^0.5 .
The value of the _(SP 22 _{-SP 12)} is, 2.00 ^{(J /} cm 3) is preferably from ^{0.5 ~10.00 (J / cm 3)} 0.5, 3.00 (J / cm ³ ) More preferably, it is ^{0.5 to} 7.00 (J / cm ³ ) ^0.5 .
The unit of the SP value in the present invention is (J / m ³ ) ^0.5 , and 1 (cal / cm ³ ) ^0.5 = 2.045 × 10 ³ (J / m ³ ) ^0.5 . cal / cm ³ ) It can be converted to a unit of ^0.5 .

By satisfying the formula (1) or the formula (2), the melting point of the polymer A is maintained without lowering the crystallinity. Thereby, both low-temperature fixability and heat-resistant storage stability are achieved.
The reason is speculated as follows.
The first monomer unit is incorporated into the polymer A, and exhibits crystallinity when the first monomer units aggregate. However, in a normal case, when another monomer unit is incorporated, crystallization is easily inhibited, so that it becomes difficult to exhibit crystallinity as a polymer. This tendency becomes remarkable when the first monomer unit and other monomer units are randomly bonded in one molecule of the polymer.
On the other hand, (SP 22 _{-SP 12)} is to use a range to become polymerizable monomer of formula (2), a random first polymerizable monomer and a second polymerizable monomer during polymerization It is considered that instead of polymerizing to a certain degree, a continuous polymerization form is taken to some extent.
When (SP ₂₂ -SP ₁₂ ) is within the range of the formula (2), the first monomer unit derived from the first polymerizable monomer in the polymer A is used because a difference in SP value exists. It is considered that the polymer part mainly containing and the polymer part mainly containing the second monomer unit derived from the second polymerizable monomer can form a phase separation state in a micro region.
Further, when (SP ₂₁ -SP ₁₁ ) is within the range of the formula (1), the first monomer unit and the second monomer unit in the polymer A form a clear phase separation state without being compatible with each other. It is considered possible.
Therefore, it is considered that a polymer site in which the first polymerizable monomer is polymerized to some extent continuously can be obtained, the crystallinity of the polymer site can be increased, and the melting point is maintained.
That is, the polymer A has a crystalline portion including the first monomer unit derived from the first polymerizable monomer, and a high polarity including the second monomer unit derived from the second polymerizable monomer. It preferably has a site (or an amorphous site).

On the other hand, it has been found that when a binder resin containing the polymer A is used in a positively chargeable toner, both low-temperature fixability and chargeability can be achieved at a high level. I'm not sure why, but I speculate as follows.
The charging phenomenon generally occurs when electrons move from a substance having a low work function to a substance having a high work function, so that the electron donor side is positively charged and the electron acceptor side is negatively charged.
Therefore, in the case of the positively chargeable toner, the electrons move from the toner to the charging member or the like, so that the toner is positively charged. In order to increase the charge amount of the toner and to start the toner quickly, it is necessary to precisely control the work function of the toner and the flow of electrons at the molecular level.

As described above, the polymer A includes a crystalline site including the first monomer unit derived from the first polymerizable monomer, and a second monomer unit derived from the second polymerizable monomer. It becomes possible to form a clear phase-separated state without causing high-polarity sites (or amorphous sites) to be compatible with each other.
The highly polar portion including the second monomer unit serves as an electron supply site, and the crystalline portion including the first monomer unit serves as an electron transfer site, so that electrons can be quickly and massively transferred from the toner to the charging member. It is possible to do.
As a result, it is considered that the toner can quickly acquire the positive charging property.
Further, in the electrophotographic process using the positively chargeable toner, considering the relationship with the work function of the charging member, when the work function of the toner is 5.0 eV to 5.4 eV, the transfer amount and the transfer speed of the electrons are reduced. I found out that it can be used to the fullest.
A toner having a work function of less than 5.0 eV is hardly obtained substantially, and a work function of more than 5.4 eV becomes a substantially negatively charged toner and cannot be applied to an electrophotographic process using a positively charged toner.
The work function of the toner is preferably from 5.0 eV to 5.3 eV.
That is, in a positively chargeable toner using a crystalline resin, the problem of compatibility between low-temperature fixability and chargeability is solved by design in consideration of electron transfer at the molecular level in the crystalline resin and control of the work function of the toner. It became possible.

If _(SP 22 _{-SP 12)} is less than ^{0.60 (J / cm 3) 0.5} , a melting point of polymer A is reduced, heat-resistant storage stability is lowered. In addition, the difference in polarity between the high-polarity part and the crystalline part is small, making it difficult to transfer electrons quickly and in large quantities, which affects the chargeability.
On the other hand, when it is larger than 15.00 (J / cm ³ ) ^0.5 , it is considered that the copolymerizability of the polymer A is inferior, non-uniformity occurs, low-temperature fixability is reduced, and the electron transfer speed is reduced. Tends to decrease.

_Similarly, if (SP 21 _{-SP 11)} is less than ^{3.00 (J / cm 3) 0.5} , a melting point of polymer A is reduced, heat-resistant storage stability is lowered. In addition, the difference in polarity between the high-polarity part and the crystalline part is small, making it difficult to transfer electrons quickly and in large quantities, which affects the chargeability.
On the other hand, when it is larger than 25.00 (J / cm ³ ) ^0.5 , it is considered that the copolymerizability of the polymer A is inferior, nonuniformity occurs, the low-temperature fixability decreases, and the electron moving speed decreases. Easy to fall.

In the case where the monomer unit satisfying the above requirements of the first monomer unit in the polymer A in the present invention are multiple types exist, the value of the SP ₁₁ in the formula (1) is the weighted average SP value of each monomer unit Value. For example, the monomer unit A having an SP value of SP ₁₁₁ is contained in an amount of A mol% based on the total number of moles of the monomer units satisfying the requirements of the first monomer unit, and the monomer unit B having an SP value of SP ₁₁₂ is included in the first monomer unit. The SP value (SP ₁₁ ) when containing (100-A) mol% based on the number of moles of the entire monomer unit satisfying the requirement of
SP ₁₁ = (SP ₁₁₁ × A + SP ₁₁₂ × (100−A)) / 100
It is. The same calculation is performed when three or more monomer units satisfying the requirements of the first monomer unit are included. Meanwhile, SP ₁₂ similarly represent the average value calculated in molar ratio of each of the first polymerizable monomer.
On the other hand, the monomer units derived from the second polymerizable monomer correspond to all the monomer units having SP ₂₁ satisfying the formula (1) with respect to SP ₁₁ calculated by the above method. Similarly, the second polymerizable monomer, any polymerizable monomer corresponds with SP ₂₂ satisfying the formula (2) with respect to SP ₁₂ calculated by the above method.
That is, when said second polymerizable monomer is 2 or more polymerisable monomers, SP ₂₁ denotes a SP value of the monomer units derived from each of the polymerizable monomer, SP ₂₁ -SP ₁₁ is determined for each monomer unit derived from the second polymerizable monomer. Similarly, _{SP 22} denotes a SP value of each of the polymerizable _monomer, SP 22 _{-SP 12} is determined for each of the second polymerizable monomer.

The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in the polymer A.
The content ratio of the first monomer unit is preferably 10.0 mol% to 60.0 mol%, more preferably 20.0 mol% to 40.0 mol%.
The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol based on the total number of moles of all the polymerizable monomers in the composition. %.
The content ratio of the first polymerizable monomer is preferably from 10.0 mol% to 60.0 mol%, more preferably from 20.0 mol% to 40.0 mol%.

The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all monomer units in the polymer A.
The content ratio of the second monomer unit is preferably 40.0 mol% to 95.0 mol%, more preferably 40.0 mol% to 70.0 mol%.
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol based on the total number of moles of all the polymerizable monomers in the composition. %.
The content ratio of the second polymerizable monomer is preferably from 40.0 mol% to 95.0 mol%, and more preferably from 40.0 mol% to 70.0 mol%.

When the content ratio of the first monomer unit in the polymer A, and the content ratio of the first polymerizable monomer in the composition is within the above range, the polymer A exhibits sharp melt properties. At the same time, elasticity near room temperature is maintained. As a result, the toner is excellent in low-temperature fixability and durability. Further, the toner has sufficient crystallinity, and enables quick electron transfer.
When each content ratio is less than 5.0 mol%, the amount of crystallization of the polymer A decreases and sharp meltability decreases, so that low-temperature fixability decreases. On the other hand, if it is more than 60.0 mol%, the elasticity near room temperature decreases, and the durability of the toner decreases.
In any case, the balance between the electron donating site and the potential transfer site is lost, and it is difficult to obtain a sufficient positive charging property.

When the content ratio of the second monomer unit in the polymer A, and the content ratio of the second polymerizable monomer in the composition is within the above range, the polymer A while maintaining sharp melt properties, The elasticity at around room temperature can be improved, and the toner is excellent in low-temperature fixability and durability. In addition, crystallization of the first monomer unit in the polymer A is not easily inhibited, and the melting point can be maintained. Further, a large amount of electrons can be provided from the second monomer unit.
When each content ratio is less than 20.0 mol%, the elasticity of the polymer A decreases, and the durability of the toner decreases. On the other hand, when it is more than 95.0 mol%, the sharp melt property of the polymer A decreases, and the low-temperature fixability decreases.
In any case, the balance between the electron donating site and the potential transfer site is lost, and it is difficult to obtain a sufficient positive charging property.

When the polymer A has a monomer unit derived from a (meth) acrylic acid ester having two or more alkyl groups having 18 to 36 carbon atoms, the content ratio of the first monomer unit is determined by calculating Represents the molar ratio. Similarly, when the composition used for the polymer A contains two or more (meth) acrylates having an alkyl group having 18 to 36 carbon atoms, the content ratio of the first polymerizable monomer is also It represents the total molar ratio of them.
When two or more monomer units derived from the second polymerizable monomer satisfying the formula (1) are present in the polymer A, the ratio of the second monomer unit is determined by the total molar ratio thereof. Represents Similarly, when the composition used for the polymer A contains two or more types of second polymerizable monomers, the content ratio of the second polymerizable monomer represents the total molar ratio thereof. .

The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylates having an alkyl group having 18 to 36 carbon atoms.
As the (meth) acrylate having an alkyl group having 18 to 36 carbon atoms, for example, a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth) acrylate, (meth) ) Nonadecyl acrylate, eicosyl (meth) acrylate, heneicosanyl (meth) acrylate, behenyl (meth) acrylate, lignoseryl (meth) acrylate, seryl (meth) acrylate, octacosa (meth) acrylate, (meth) And a (meth) acrylic ester having a branched alkyl group having 18 to 36 carbon atoms [such as 2-decyltetradecyl (meth) acrylate].
Among these, from the viewpoint of storage stability of the toner, it is preferably at least one selected from the group consisting of (meth) acrylates having a linear alkyl group having 18 to 36 carbon atoms. More preferably, it is at least one selected from the group consisting of (meth) acrylates having a linear alkyl group having 18 to 30 carbon atoms. More preferably, it is at least one selected from the group consisting of linear stearyl (meth) acrylate and behenyl (meth) acrylate.
As the first polymerizable monomer, one type may be used alone, or two or more types may be used in combination.

Examples of the second polymerizable monomer include, among the polymerizable monomers listed below, a polymerizable monomer that satisfies the formula (1) or the formula (2).
As the second polymerizable monomer, one type may be used alone, or two or more types may be used in combination.
Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile and the like.
Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like.
A monomer having an amide group; for example, acrylamide, an amine having 1 to 30 carbon atoms and a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) are reacted by a known method. Monomer.

Monomer having a urethane group: for example, an alcohol having an ethylenically unsaturated bond and having 2 to 22 carbon atoms (such as 2-hydroxyethyl methacrylate and vinyl alcohol) and an isocyanate having 1 to 30 carbon atoms [monoisocyanate compound (Benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl Isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-dipropylphenyl isocyanate, etc.) Aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. ), Alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated Added tetramethyl xylylene diisocyanate) And aromatic diisocyanate compounds (phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-toluidine diisocyanate, , 4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate, etc.) and a C1-C26 alcohol. (Methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, Decyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, hen Eicosanol, behenyl alcohol, erucyl alcohol, etc.) and an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms [2-isocyanatoethyl (meth) acrylate, (meth) acrylic acid 2- (0- [1 '-Methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyl Oxymethyl) ethyl isocyanate] with a known method.

Monomers having a urea group: for example, amines having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine and isopropylamine), and secondary amines (dinalethylamine, dinormalpropylamine, diamine A normal butylamine, etc.), aniline and cycloxylamine, etc.] and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method.
Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth) acrylate.
Among them, it is preferable to use a monomer having a nitrile group, an amide group, a urethane group, a hydroxy group, or a urea group. More preferably, the second polymerizable monomer is a single monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxy group, a urethane group, and a urea group, and an ethylenically unsaturated bond. Is a monomer.
By having these, the melting point of the polymer A is easily increased, and the heat-resistant storage stability is easily improved. In addition, the elasticity near room temperature is increased, and the durability is easily improved.

As the second polymerizable monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, pivalic acid Vinyl esters such as vinyl and vinyl octylate are also preferably used. Vinyl esters are non-conjugated monomers, and the reactivity with the first polymerizable monomer is easily maintained at an appropriate level. Therefore, it is considered that a state in which monomer units derived from the first polymerizable monomer are aggregated and bonded in the polymer A is likely to be formed, and the crystallinity of the polymer A is increased, and low-temperature fixability and heat resistance are improved. It is easier to balance the preservability.
The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
Further, it is preferable that the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

In the formulas A and B, X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (—C≡N),
An amide group (—C (＝ O) NHR ¹⁰ , wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy group,
—COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms, or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),
A urethane group (—NHCOOR ¹² , wherein R ¹² is an alkyl group having 1 to 4 carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ , wherein each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms);
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms)
Is shown.
Preferably, R ¹ is a nitrile group (—C≡N),
An amide group (—C (＝ O) NHR ¹⁰ , wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy group,
—COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms, or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ , wherein each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms);
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms)
Is shown.
R ² represents an alkyl group having 1 to 4 carbon atoms,
R ³ each independently represents a hydrogen atom or a methyl group.

  The polymer A is preferably a vinyl polymer. The vinyl polymer includes, for example, a polymer of a monomer containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of undergoing radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

Polymer A, the first monomer unit derived from the first polymerizable monomer described above, in a range that does not impair the molar ratio of the second monomer unit derived from the second polymerizable monomer,
It may contain a third monomer unit derived from a third polymerizable monomer different from the first polymerizable monomer and the second polymerizable monomer.
Further, the first polymerizable monomer, and a composition containing a second polymerizable monomer different from the first polymerizable monomer, the first in the composition in the composition In a range that does not impair the content ratio of the polymerizable monomer, and the content ratio of the second polymerizable monomer,
It may contain a third polymerizable monomer different from the first polymerizable monomer and the second polymerizable monomer.
At this time, when the SP value of the third monomer unit is set to SP ₃₁ (J / cm ³ ) ^0.5 ,
It is preferable to satisfy the relationship of the following expression (3).
_{0.00 <(SP 31 -SP 11)} <3.00 (3)
When the SP value of the third polymerizable monomer is set to SP ₃₂ (J / cm ³ ) ^0.5 ,
It is preferable to satisfy the relationship of the following expression (4).
_{0.00 <(SP 32 -SP 12)} <0.60 (4)
As the third polymerizable monomer, a monomer satisfying the formula (3) or the formula (4) among the monomers exemplified as the second polymerizable monomer may be used.
Incidentally, the monomer unit derived from a third polymerizable monomer, all monomer units having the SP ₃₁ which satisfies the equation (3) to the SP ₁₁ corresponds. Similarly, third polymerizable monomer, a polymerizable monomer having a SP ₃₂ satisfying the equation (4) with respect to SP ₁₂ all corresponds.
That is, when said third polymerizable monomer is 2 or more polymerisable monomers, SP ₃₁ denotes a SP value of the monomer units derived from each of the polymerizable monomer, SP ₃₁ -SP ₁₁ is determined for each monomer unit derived from the third polymerizable monomer. Similarly, _{SP 32} denotes a SP value of each of the polymerizable _monomer, SP 32 _{-SP 12} is determined for each of the second polymerizable monomer.
As the third polymerizable monomer, for example, the following can be used.
Styrene and its derivatives such as o-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; Such (meth) acrylates.
In addition, since the monomer does not have a polar group, the SP value is low, and it is difficult to satisfy the above formula (1) or formula (2). However, when Formula (1) or Formula (2) is satisfied, it can be used as the second polymerizable monomer.
The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate in order to improve the storage stability of the toner.

Further, the polymer A is derived from a fourth polymerizable monomer different from the first polymerizable monomer, the second polymerizable monomer, and the third polymerizable monomer. It may have four monomer units.
It is preferable that the fourth monomer unit contains a monomer unit derived from a macromonomer.
In addition, the macromonomer is a polymer having a functional group at the terminal capable of acting as a monomer molecule, and means a polymer constituting only one kind of monomer unit in the produced polymer.
The macromonomer preferably has an acryloyl group or a methacryloyl group at a molecular chain terminal. A methacryloyl group is more preferable from the viewpoint of easy copolymerization.
The number average molecular weight of the macromonomer is preferably from 1,000 to 20,000.
The first polymerizable monomer, the second polymerizable monomer, and the third polymerizable monomer do not belong to the definition of the macromonomer, and have a number average molecular weight of 1 Less than 2,000 polymerizable monomers.
The content ratio of the monomer unit derived from the macromonomer in the polymer A is from 1.0 × 10 ⁻⁴ mol% to 3.0 ×, based on the total number of moles of all the monomer units in the polymer A. It is preferably 10 ^-1 mol%, more preferably 1.0 × 10 ⁻³ mol% to 1.0 × 10 ⁻² mol%.
When the content ratio of the monomer unit derived from the macromonomer is within the above range, the effects described later are sufficiently obtained, and it is easy to suppress non-uniformity during polymerization.
The number of moles of the macromonomer or the monomer unit derived from the macromonomer is calculated based on the number average molecular weight (Mn) of the macromonomer.
Further, the content ratio of the macromonomer in the polymer A is preferably 0.01 parts by mass to 1.0 part by mass with respect to 100 parts by mass of all the polymerizable monomers in the composition. More preferably, the amount is from 1 part by mass to 1.0 part by mass.

The macromonomer has a relatively long linear polymer having a number average molecular weight of 1,000 to 20,000 having a polymerizable functional group (for example, an unsaturated group such as a carbon-carbon double bond) at a molecular chain terminal. It is a high molecular weight monomer.
In the case of having a monomer unit derived from the macromonomer, branching of a long linear molecule derived from the monomer unit occurs in a molecular chain.
And the self-aggregation of the monomer unit having the long linear molecule facilitates the formation of a microphase-separated structure. As a result, the first monomer unit is easily oriented, and the crystalline site is easily maintained. Further, the moving speed of the electrons is further improved, and the rising of the positive charge becomes faster even in a high-temperature and high-humidity environment where the chargeability is more severe.
When the number average molecular weight of the macromonomer is 1,000 to 20,000, a branched structure (also referred to as a graft structure) is easily moved, and a microphase-separated structure is easily obtained.
Examples of the component constituting the long linear molecule include styrene, styrene derivatives, methacrylates, acrylates, acrylonitrile, methacrylonitrile, and the like, or a polymer obtained by polymerizing two or more kinds; Examples having a siloxane skeleton can be given.
Among them, it is preferable that the macromonomer is at least one selected from the group consisting of a (meth) acrylate polymer having an acryloyl group or a methacryloyl group at a molecular chain terminal. By using a (meth) acrylate polymer, the cohesiveness is further enhanced, and the crystalline portion of the first monomer unit is more easily retained.

The toner preferably contains at least one selected from the group consisting of a positive charge control agent and a positive charge control resin.
By using a positively chargeable charge control agent or a positively chargeable charge control resin and adjusting the addition amount, the work function of the entire toner can be easily controlled within the above range. Further, since the positive charge control agent and the positive charge control resin also serve as electron donating sites, a higher charge amount can be obtained.
Examples of the positive charge control agent include a nigrosine dye, a quaternary ammonium salt, a triaminotriphenylmethane compound, and an imidazole compound.
Examples of the positively chargeable charge control resin include a polyamine resin, a quaternary ammonium group-containing copolymer, and a quaternary ammonium base-containing copolymer. Among them, a charge control resin having good dispersibility in the toner is preferable, and a quaternary ammonium base-containing copolymer (for example, a quaternary ammonium base-containing styrene acrylic resin) is more preferable.
Further, since the work function of the toner is easily affected by the surface of the toner particles, it is preferable that the positively-charged charge control agent and the charge control resin exist on the outermost surface of the toner particles.
For example, in a toner having a core-shell structure, the shell agent preferably contains a positively-chargeable charge control agent or charge control resin.
The content of the charge control agent and / or the charge control resin is preferably 0.01 to 10 parts by mass, and more preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, there is. These charge control agents and charge control resins can be used alone or in combination of two or more.

The toner particles may contain a release agent.
Examples of the release agent include waxes mainly containing a fatty acid ester such as carnauba wax and montanic acid ester wax; a part or all of an acid component is deoxidized from a fatty acid ester such as a deoxidized carnauba wax. Methyl ester compounds having a hydroxy group obtained by hydrogenation of vegetable fats and oils; saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; dibehenyl sebacate, distearyl dodecane diacid, di octadecane diacid Diester of a saturated aliphatic dicarboxylic acid such as stearyl and a saturated aliphatic alcohol; diester of a saturated aliphatic diol such as nonanediol dibehenate and dodecanediol distearate with a saturated fatty acid; low molecular weight polyethylene; low molecular weight polypropylene , My Aliphatic hydrocarbon waxes such as locrystallin wax, paraffin wax and Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; styrene and aliphatic hydrocarbon waxes Waxes grafted with vinyl monomers such as acrylic acid; saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and parinaric acid; Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melisyl alcohol; polyhydric alcohols such as sorbitol; linoleamide, oleamide, lauric acid Fatty acid amides such as amides; saturated fatty acid amides such as methylenebisstearic acid amide, ethylenebiscapramide, ethylenebislauric amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide And unsaturated fatty acid amides such as N, N'-dioleyl adipamide and N, N'-dioleyl sebacamide; and m-xylene bisstearic acid amide and N, N'-distearyl isophthalic amide. Aromatic bisamides; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (commonly referred to as metallic soaps); long-chain alkyl alcohols having 12 or more carbon atoms or long-chains Alkyl carboxylic acid; And so on.
The content of the release agent in the toner particles is preferably from 1.0% by mass to 30.0% by mass, and more preferably from 2.0% by mass to 25.0% by mass.

The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component of the polymer A measured by gel permeation chromatography (GPC) is preferably 10,000 to 200,000, and 20,000 to 150. More preferably, it is 2,000.
When the weight average molecular weight (Mw) is in the above range, elasticity near room temperature is easily maintained.
Further, the melting point of the polymer A is preferably from 50C to 80C, more preferably from 53C to 70C. When the melting point is in the above range, low-temperature fixability and heat-resistant storage stability are further improved.
The melting point of the polymer A can be adjusted depending on the type and amount of the first polymerizable monomer used, the type and amount of the second polymerizable monomer, and the like.

The content of the polymer A in the binder resin is preferably 50.0% by mass or more.
When the content is 50.0% by mass or more, the sharp melt property of the toner is easily maintained, and the low-temperature fixability is improved. Further, the positive charging property can be obtained more stably.
The content is more preferably 80.0% by mass to 100.0% by mass, and further preferably the binder resin is the polymer A.
Examples of resins that can be used other than the polymer A as the binder resin include conventionally known vinyl resins, polyester resins, polyurethane resins, and epoxy resins. Among them, vinyl resins, polyester resins and polyurethane resins are preferred from the viewpoint of electrophotographic properties.
The polymerizable monomer that can be used for the vinyl resin is a polymerizable monomer that can be used for the first polymerizable monomer, the second polymerizable monomer, and the third polymerizable monomer described above. Body and the like. If necessary, two or more kinds may be used in combination.

The polyester resin can be obtained by reacting a divalent or higher polyvalent carboxylic acid with a polyhydric alcohol.
Examples of the polyvalent carboxylic acid include the following compounds. Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenylsuccinic acid, and their anhydrides or lower alkyl esters thereof; and maleic acid, fumaric acid, Aliphatic unsaturated dicarboxylic acids such as itaconic acid and citraconic acid.
1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and anhydrides or lower alkyl esters thereof. These may be used alone or in combination of two or more.

Examples of the polyhydric alcohol include the following compounds. Alkylene glycols (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A): Alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portion of the alkylene glycol and the alkylene ether glycol may be linear or branched. Further, glycerin, trimethylolethane, trimethylolpropane and pentaerythritol. These may be used alone or in combination of two or more.
For the purpose of adjusting the acid value and the hydroxyl value, a monovalent acid such as acetic acid and benzoic acid, and a monohydric alcohol such as cyclohexanol and benzyl alcohol can be used as necessary.
The method for producing the polyester resin is not particularly limited. For example, a transesterification method or a direct polycondensation method can be used alone or in combination.

Next, the polyurethane resin will be described. The polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and a resin having various functions can be obtained by adjusting the diol and the diisocyanate.
The following are mentioned as a diisocyanate component. Aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic diisocyanate having 2 to 18 carbon atoms, alicyclic diisocyanate having 4 to 15 carbon atoms, and these diisocyanates (Modified products containing a urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group; hereinafter also referred to as "modified diisocyanate"); A mixture of two or more of the above.

Examples of the aromatic diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate.
The following are examples of the aliphatic diisocyanate. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and dodecamethylene diisocyanate.
The following are examples of the alicyclic diisocyanate. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are XDI , IPDI and HDI.
Further, in addition to the diisocyanate component, a tri- or higher functional isocyanate compound can be used.
As the diol component that can be used for the polyurethane resin, the same diol component as the divalent alcohol that can be used for the polyester resin described above can be used.

The toner particles may contain a colorant. Examples of the coloring agent include known organic pigments, organic dyes, inorganic pigments, carbon black as a black coloring agent, and magnetic substances. In addition, colorants conventionally used in toners may be used.
Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.
Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are preferably used.

The following are examples of the cyan colorant. Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are preferably used.
The colorant is selected from the viewpoints of hue angle, saturation, lightness, light fastness, OHP transparency, and dispersibility in the toner.
The content of the colorant is preferably 1.0 to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin. When a magnetic material is used as the colorant, the amount added is preferably 40.0 parts by mass to 150.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner particles may have a core-shell structure in which a shell is formed on the surface of the core particles.
The method for forming the core-shell structure is not particularly limited. For example, it is preferable to form a polymerized layer serving as a shell by subjecting a polymerizable monomer for shell to suspension polymerization in the presence of core particles.
As the polymerizable monomer for the shell, it is preferable to use monomers that form a polymer having a glass transition temperature exceeding 70 ° C., such as styrene and methyl methacrylate, alone or in combination of two or more. Methyl methacrylate is more preferred.
The glass transition temperature of the polymer obtained from the polymerizable monomer for shell is preferably from 50 ° C to 120 ° C, more preferably from 60 ° C to 110 ° C, in order to improve the storage stability of the toner. , 70 ° C to 105 ° C.

Further, the shell may include a thermosetting resin from the viewpoint of heat resistance.
The following can be exemplified as the thermosetting resin.
Melamine resin, urea (urea) resin, sulfonamide resin, glyoxal resin, guanamine resin, aniline resin, or derivatives of these resins.
Polyimide resin; maleimide polymers such as bismaleimide, aminobismaleimide, and bismaleimide triazine.
A resin (hereinafter, referred to as an aminoaldehyde resin) formed by polycondensation of a compound containing an amino group with an aldehyde (for example, formaldehyde), or a derivative of an aminoaldehyde resin.
The melamine resin is a polycondensate of melamine and formaldehyde. Urea resin is a polycondensate of urea and formaldehyde. Glyoxal resin is a polycondensate of a reaction product of glyoxal and urea with formaldehyde. As the glyoxal resin, dimethylol dihydroxyethylene urea (DMDHEU) is preferable.
By adding a nitrogen element to the thermosetting resin, the crosslinking and curing function of the thermosetting resin can be improved. In order to increase the reactivity of the thermosetting resin, the content of the nitrogen element is reduced to 40% by mass or more and 55% by mass or less for the melamine resin, approximately 40% by mass for the urea resin, and approximately 15% by mass for the glyoxal resin. Adjustment is preferred.
For the preparation of the thermosetting resin contained in the shell, one or more thermosetting monomers selected from the group consisting of methylol melamine, melamine, methylolated urea, urea, benzoguanamine, acetoguanamine, and spiroguanamine are preferably used. Can be used.

For forming the shell, a curing agent or a reaction accelerator may be used, or a polymer in which a plurality of functional groups are combined may be used. Further, the water resistance of the shell may be improved by using an acrylic silicone resin (graft polymer).
The thickness of the shell is preferably 20 nm or less, more preferably 3 nm to 20 nm. The formation of the shell is preferably performed in an aqueous medium, and the material of the shell is preferably water-soluble.

In order to form a shell with a thermosetting resin, it is preferable that the core particles have an anionic property and the shell has a cationic property. The anionic nature of the core particles allows the cationic shell material to be attracted to the surface of the core particles during shell formation.
Specifically, for example, a shell material positively charged in the aqueous medium is electrically attracted to the core particles negatively charged in the aqueous medium, and a shell is formed on the surface of the core particles by in-situ polymerization. This makes it easier to form a uniform shell on the surface of the core particles without excessively dispersing the core particles in the aqueous medium using the dispersant.
The shell preferably contains a positively chargeable charge control agent and / or a positively chargeable charge control resin in order to control the work function of the toner.

The toner preferably contains an external additive in order to improve charge stability, developability, fluidity, and durability. Examples of the external additive include silica fine particles and inorganic fine particles such as metal oxide fine particles (such as alumina fine particles, titanium oxide fine particles, magnesium oxide fine particles, zinc oxide fine particles, strontium titanate fine particles, and barium titanate fine particles).
Further, organic fine particles made of a vinyl resin, a silicone resin, a melamine resin, or the like, and organic-inorganic composite fine particles may be used.
The content of the external additive is preferably from 0.1 to 4.0 parts by mass, and more preferably from 0.2 to 3.5 parts by mass, based on 100.0 parts by mass of the toner particles. Is more preferred.

The external additive is preferably surface-treated in order to control the work function of the toner. For example, when silica particles are used as the external additive particles, it is preferable that the surface of the silica particles is given a positive charge by a surface treatment agent.
Examples of the surface treatment agent include silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other treatment agents such as organic silicon compounds and organic titanium compounds. These may be used alone or in combination.
Among them, treatment with a silane compound having a substituent having a nitrogen element (particularly, an amino group) or silicone oil is preferred from the viewpoint of controlling the toner work function.
Specific examples of the surface treatment agent having an amino group include an amino group-containing coupling agent, and an amino-modified silicone oil modified by introducing an amino group into a side chain or terminal of the silicone oil.
The treatment amount using the surface treatment agent is preferably 0.02 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, and still more preferably 100 parts by mass of the external additive. Is 0.1 to 2 parts by mass.

When the toner is mixed with a magnetic carrier to form a two-component developer and application to a two-component developer system is considered, the external additive preferably has a conductive layer on its surface.
In a two-component developing system, charging is performed using a magnetic carrier. However, in the case of charging using a magnetic carrier, the charging distribution is likely to be broad and fog is likely to occur. Therefore, by using an external additive having a conductive layer on the surface, excessive charge-up of the toner can be suppressed, and the charge distribution can be sharpened.
Further, it is preferable that the conductive layer is a film forming body containing tin oxide (SnO ₂ ) doped with antimony (Sb). By having the conductive layer, the mobility of electrons can be further increased, so that it is easy to achieve both a charge rising property and a sharp charge distribution.
The volume resistivity of the external additive having a conductive layer is preferably ^{1.0 × 10 0 Ω · cm~1.0 ×} 10 7 Ω · cm or so. The number average particle diameter of the primary particles of the external additive having the conductive layer is preferably 0.01 μm to 1.00 μm, and more preferably 0.10 μm to 0.80 μm.

Here, a specific method of providing a conductive layer will be described using titanium oxide as an example.
First, a mixture of titanium tetrachloride and oxygen gas obtained by the chlorine method is introduced into a gas phase oxidation reactor, and reacted at a temperature of 1000 ° C. in a gas phase to obtain a bulk of titanium oxide. The obtained titanium oxide bulk is pulverized by a hammer mill or the like, washed, dried at a temperature of 110 ° C., and then pulverized by a jet mill or the like to obtain titanium oxide fine particles.
The number average particle diameter of the primary particles of titanium oxide can be adjusted by changing the conditions for pulverizing the bulk of titanium oxide with a hammer mill or the like.
Next, titanium oxide fine particles are dispersed in water so that the concentration becomes about 50 g / L, and sodium pyrophosphate is further added. The mixture is wet-ground with a sand mill or the like to prepare a water-soluble slurry.
Then, after heating the obtained water-soluble slurry to 80 ° C., a mixed solution in which an appropriate amount of tin chloride (SnCl ₄ .5H ₂ O) and antimony chloride (SbCl ₃ ) is dissolved in a 2 mol / L hydrochloric acid solution (300 mL) And a 10% by mass sodium hydroxide solution were added over 60 minutes while maintaining the pH at 6 to 9 to form a film containing tin oxide doped with antimony, which is a conductive layer, on the surface of the titanium oxide fine particles. To form titanium oxide fine particles having a conductive layer.

The toner particles may be produced by any conventionally known method such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, and a pulverization method as long as the toner particles fall within the range of the present configuration. It is preferably manufactured.
For example, a polymerizable monomer that forms a binder resin containing the polymer A, and other additives such as a release agent and a colorant, if necessary, are mixed to obtain a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is added to an aqueous medium (a dispersion stabilizer may be contained if necessary). Then, particles of the polymerizable monomer composition are formed in an aqueous medium, and the polymerizable monomer contained in the particles is polymerized. By doing so, toner particles can be obtained.

Next, methods for measuring physical properties according to the present invention will be described.
<Method for measuring content ratio of monomer units derived from various polymerizable monomers in polymer A>
The measurement of the content ratio of the monomer units derived from various polymerizable monomers in the polymer A is performed by ¹ H-NMR under the following conditions.
-Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
・ Measurement frequency: 400MHz
・ Pulse condition: 5.0 μs
・ Frequency range: 10500Hz
・ Total number of times: 64 ・ Measurement temperature: 30 ℃
Sample: 50 mg of a sample to be measured is placed in a sample tube having an inner diameter of 5 mm, and chloroform (CDCl ₃ ) is added as a solvent and dissolved in a 40 ° C. constant temperature bath.
From the obtained ¹ H-NMR chart, among peaks attributed to the constituent elements of the monomer unit derived from the first polymerizable monomer, peaks attributed to the constituent elements of the monomer unit derived from the other are selects the independent peaks, calculates an integrated values S ₁ for the peak.
Similarly, from among the peaks attributed to the components of the monomer unit derived from the second polymerizable monomer, a peak independent of the peak attributed to the components of the monomer unit derived from the other is selected. , an integrated value S ₂ is calculated for this peak.
Furthermore, when a third or fourth polymerizable monomer is used, the peaks attributed to the constituent elements of the monomer unit derived from the third or fourth polymerizable monomer are derived from the other. the peak attributable to the components of the monomer unit selects the independent peaks, integrating values S ₃ and S ₄ is calculated for this peak.

The content ratio of the monomer unit derived from the first polymerizable monomer is determined as follows using the above integral values S ₁ , S ₂ , S ₃ and S ₄ . Note that n ₁ , n ₂ , n ₃ , and n ₄ are the numbers of hydrogen in the constituent elements to which the peaks of interest are assigned for each site.
Content ratio (mol%) of monomer units derived from the first polymerizable monomer =
｛(S ₁ / n ₁ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ) + (S ₄ / n ₄ )
)｝ × 100
Similarly, the content ratio of the monomer units derived from the second polymerizable monomer, the third polymerizable monomer, and the fourth polymerizable monomer is determined as follows.
Content ratio (mol%) of monomer units derived from the second polymerizable monomer =
｛(S ₂ / n ₂ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ) + (S ₄ / n ₄ )
)｝ × 100
Content ratio (mol%) of monomer unit derived from third polymerizable monomer =
｛(S ₃ / n ₃ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ) + (S ₄ / n ₄ )
)｝ × 100
Content ratio (mol%) of monomer unit derived from fourth polymerizable monomer =
｛(S ₄ / n ₄ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ) + (S ₄ / n ₄ ))
｝ × 100
When a polymerizable monomer containing no hydrogen atom in the constituents other than the vinyl group is used in the polymer A, the measured nuclei are set to ¹³ C by ¹³ C-NMR, and the single pulse mode is used. , And similarly calculated by ¹ H-NMR.
Further, when the toner particles are produced by a suspension polymerization method, the peaks of the release agent and other resins may overlap, and an independent peak may not be observed. As a result, the content of monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In this case, by performing the same suspension polymerization without using a release agent or another resin, the polymer A ′ can be manufactured, and the polymer A ′ can be analyzed as the polymer A.

<Method of calculating SP value>
SP ₁₂ , SP ₂₂ and SP ₃₂ are calculated according to the calculation method proposed by Fedors.
It is obtained as follows.
For each polymerizable monomer, the evaporation energy (Δei) from the table described in “polym. Eng. Sci., 14 (2), 147-154 (1974)” with respect to the atom or atomic group in the molecular structure. ) (Cal / mol) and molar volume (Δvi) (cm ³ / mol) are determined, and (4.184 × ΣΔei / ΣΔvi) ^0.5 is defined as SP value (J / cm ³ ) ^0.5 .
On the other hand, SP ₁₁ , SP ₂₁ , and SP ₃₁ are calculated by the same calculation method as described above for the atoms or atomic groups of the molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.

<Method for measuring work function of toner>
The work function of the toner is measured by the following measuring method.
The work function is quantified as energy (eV) for extracting electrons from the substance.
The work function is measured using a surface analyzer (AC-2 manufactured by Riken Keiki Co., Ltd.).
In this apparatus, a deuterium lamp was used, the set value of the irradiation light amount was 800 nW, monochromatic light was selected by a spectroscope, the spot size was 4 [mm] × 4 [mm], and the energy scanning range was 3.6 to 6.2. The sample is irradiated at [eV], anode voltage: 2910 V, and measurement time of 10 [sec / 1 point].
Then, photoelectrons emitted from the surface of the sample are detected, and arithmetic processing is performed using work function calculation software incorporated in the surface analyzer. The work function is measured with a repeatability (standard deviation) of 0.02 [eV]. When measuring powder, a cell for powder measurement is used.
FIG. 1 is a schematic diagram of a cell for measuring powder. (A) is a plan view of the cell 10, (b) is a partially cutaway side view, and (c) is a perspective view. The cell 10 has a sample receiving recess 10a having a diameter of 15 mm and a depth of 3 mm in the center of a stainless steel disk having a diameter of 30 mm and a height of 5 mm.
After placing the sample in the sample accommodating recess 10a without squeezing using a weighing sag, the measuring cell is placed on a specified position of the sample table with the surface leveled and flattened using a knife edge. Fix and measure.
In the surface analysis, when the excitation energy of monochromatic light is scanned from the lower side to the higher side at intervals of 0.1 eV, photon emission starts from a certain energy value [eV], and this energy threshold is defined as a work function [eV]. I do.
FIG. 2 shows an example of a work function measurement curve obtained by the measurement under the above conditions.
In FIG. 2, the horizontal axis represents the excitation energy [eV], and the vertical axis represents the value (normalized photon yield) Y of the number of emitted photoelectrons to the 0.5 power. Generally, when the excitation energy value exceeds a certain threshold value, the emission of photoelectrons, that is, the normalized photon quantum yield increases, and the work function measurement curve rapidly rises. The rising point is defined as the photoelectric work function value [Wf]. This photoelectric work function value [Wf] was defined as the work function of the toner.

<Method for measuring weight average molecular weight (Mw) of polymer A>
The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble portion of the polymer A is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maisho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. The measurement is performed under the following conditions using this sample solution.
-Equipment: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
-Column: Shodex KF-801, 802, 803, 804, 805, 806, 8
07 7 stations (Showa Denko KK)
・ Eluent: tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
・ Oven temperature: 40.0 ° C
・ Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, a standard polystyrene resin (trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ”, manufactured by Tosoh Corporation).

<Measurement method of melting point>
The melting points of the polymer A and the release agent are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Heating rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of the calorific value uses the heat of fusion of indium.
Specifically, 5 mg of a sample is precisely weighed, placed in an aluminum pan, and subjected to differential scanning calorimetry. An empty silver pan is used as a reference.
The peak temperature of the maximum endothermic peak in the first heating process is the melting point (° C.).
Note that the maximum endothermic peak is a peak at which the amount of endotherm becomes maximum when there are a plurality of peaks.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following formulations, "parts" are based on mass unless otherwise specified.

<Preparation of monomer having urethane group>
50.0 parts of methanol was charged to the reaction vessel. Thereafter, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko KK) was added dropwise at 40 ° C. with stirring. After completion of the dropwise addition, stirring was performed for 2 hours while maintaining the temperature at 40 ° C. Thereafter, a monomer having a urethane group was prepared by removing unreacted methanol with an evaporator.

<Preparation of monomer having urea group>
50.0 parts of dibutylamine was charged to the reaction vessel. Thereafter, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] was added dropwise at room temperature under stirring. After completion of the dropwise addition, stirring was performed for 2 hours. Then, a monomer having a urea group was prepared by removing unreacted dibutylamine with an evaporator.

<Preparation of polymer A0>
The following materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere.
・ Toluene 100.0 parts ・ Monomer composition 100.0 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile and styrene in the proportions shown below)
-Behenyl acrylate (first polymerizable monomer) 67.0 parts (28.9 mol%)
-Methacrylonitrile (second polymerizable monomer) 22.0 parts (53.8 mol%)
-Styrene (third polymerizable monomer) 11.0 parts (17.3 mol%)
0.5 parts of t-butyl peroxypivalate (polymerization initiator, manufactured by NOF Corporation: Perbutyl PV)
The polymerization reaction was performed for 12 hours by heating to 70 ° C. while stirring the inside of the reaction vessel at 200 rpm to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate a methanol-insoluble component. The obtained methanol-insoluble matter was separated by filtration, further washed with methanol, and vacuum-dried at 40 ° C. for 24 hours to obtain a polymer A0. The weight average molecular weight (Mw) of the polymer A0 was 68,400, the acid value was 0.0 mgKOH / g, and the melting point was 62 ° C.
When the polymer A0 was analyzed by NMR, the monomer unit derived from behenyl acrylate was 28.9 mol%, the monomer unit derived from methacrylonitrile was 53.8 mol%, and the monomer unit derived from styrene was 17.3 mol%. Was included.

<Preparation of amorphous resin>
The following raw materials were charged into a heated and dried two-necked flask while introducing nitrogen.
・ Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
30.0 parts polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
33.0 parts, terephthalic acid 21.0 parts, dodecenylsuccinic acid 15.0 parts, dibutyltin oxide 0.1 part After the inside of the system was purged with nitrogen by a reduced pressure operation, the mixture was stirred at 215 ° C for 5 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and further maintained for 2 hours. When the mixture became viscous, the mixture was air-cooled to stop the reaction, thereby synthesizing an amorphous resin as an amorphous polyester. The amorphous resin had a number average molecular weight (Mn) of 5,200, a weight average molecular weight (Mw) of 23,000, and a glass transition temperature (Tg) of 55 ° C.

<Production Example of Toner 1>
[Production of toner by suspension polymerization method]
(Production of toner particles 1)
・ Monomer composition 100.0 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, styrene, and macromonomer in the ratio shown below)
-Behenyl acrylate (first polymerizable monomer) 66.8 parts (28.87 mol%)
-Methacrylonitrile (second polymerizable monomer) 21.9 parts (53.79 mol%)
・ Styrene 11.0 parts (17.33 mol%)
.0.3 parts of polymethyl methacrylate having a methacryloyl group at a terminal
(8.2 × 10 ⁻³ mol%) (macromonomer, manufactured by Toagosei Co., Ltd., AA-6, Mn: 6,000)
-Pigment Blue 15: 3 6.5 parts-Charge control resin 0.7 part (quaternary ammonium salt-containing styrene-acrylic acid resin, "FCA-201-PS"
Fujikura Chemical Co., Ltd.)
・ 20.0 parts of release agent (trade name: HNP-51, melting point: 78 ° C, manufactured by Nippon Seiro)
A mixture consisting of 100.0 parts of toluene was prepared. The mixture was charged into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads having a diameter of 5 mm to obtain a raw material dispersion.
On the other hand, at room temperature, an aqueous solution obtained by dissolving 10.2 parts of magnesium chloride (water-soluble polyvalent metal salt) in 250 parts of ion-exchanged water, and sodium hydroxide (alkali metal hydroxide) 6.2 in 50 parts of ion-exchanged water. The aqueous solution in which the parts were dissolved was gradually added under stirring to prepare a dispersion of a magnesium hydroxide colloid (a poorly water-soluble metal hydroxide colloid).
The polymerizable monomer composition was added to the magnesium hydroxide colloid dispersion at room temperature and stirred. After adding 8.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator, an in-line emulsifying / dispersing machine (manufactured by Taiheiyo Kiko Co., Ltd., trade name: Milder) is used. Then, dispersion was performed by high-speed shearing and stirring at a rotation speed of 15,000 rpm for 10 minutes to form droplets of the polymerizable monomer composition.
The obtained granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and heated to 70 ° C. while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was performed at 150 rpm for 10 hours while maintaining 70 ° C. Thereafter, the reflux condenser was removed from the reaction vessel, the temperature of the reaction solution was raised to 95 ° C., and the mixture was stirred at 150 rpm for 5 hours while maintaining the temperature at 95 ° C. to remove toluene, thereby obtaining a toner particle dispersion.
While stirring the obtained toner particle dispersion, sulfuric acid was added dropwise at room temperature, and acid washing was performed until the pH became 6.5 or less. Next, filtration separation was performed, and 500 parts of ion-exchanged water was added to the obtained solid to reslurry, and a water washing treatment (washing, filtration, and dehydration) was repeated several times. Next, filtration and separation were performed, and the obtained solid content was placed in a container of a drier and dried at 40 ° C. for 24 hours to obtain toner particles 1 containing polymer A1 of the monomer composition.
Further, a polymer A1 ′ was obtained in the same manner as the toner particle 1 except that Pigment Blue 15: 3, a charge control resin, and a release agent were not used.
The weight average molecular weight (Mw) of the polymer A1 ′ was 57,000 and the melting point was 62 ° C.
When the polymer A1 was analyzed by NMR, the monomer unit derived from behenyl acrylate was 28.87 mol%, the monomer unit derived from methacrylonitrile was 53.79 mol%, the monomer unit derived from styrene was 17.33 mol%, And 8.2 × 10 ⁻³ mol% of macromonomer.
Since the polymer A1 and the polymer A1 ′ were produced in the same manner, it was determined that they had the same physical properties.

(Preparation of Toner 1)
The toner particles 1 were externally added. For 100.0 parts of toner particles 1, 0.7 parts of silica fine particles 1 (silica fine particles having a number-average particle diameter of primary particles of 10 nm which has been subjected to hydrophobic treatment with amino-modified silicone oil) 0.7 parts and silica fine particles 2 (amino Toner 1 was obtained by dry-mixing 1.0 part of a primary particle (a silica fine particle having a number-average particle diameter of 55 nm of a primary particle hydrophobically treated with a modified silicone oil) of 5 minutes with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Table 2 shows the physical properties of Toner 1 thus obtained.

<Production Examples of Toners 2 to 27>
In the production example of the toner 1, the toner particles 2 to 2 were prepared in the same manner except that the types and the amounts of the polymerizable monomer, the macromonomer, and the charge control agent or the charge control resin used were changed as shown in Table 1. 27 was obtained.
In the production example of the toner 25, a macromonomer (AK-32, manufactured by Toagosei Co., Ltd., Mn: 20,000) having dimethylsiloxane as a main skeleton and having a methacryloyl group at a terminal was used.
Further, the same external addition as in the production example of Toner 1 was performed to obtain Toners 2 to 27. Table 2 shows the physical properties of Toners 2 to 27.

<Production Example of Toner 28>
・ Monomer composition 100.0 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, styrene and macromonomer in the proportions shown below)
-Behenyl acrylate (first polymerizable monomer) 66.8 parts (28.87 mol%)
-Methacrylonitrile (second polymerizable monomer) 21.9 parts (53.79 mol%)
・ Styrene 11.0 parts (17.33 mol%)
.0.3 parts of polymethyl methacrylate having a methacryloyl group at a terminal
(8.2 × 10 ⁻³ mol%) (macromonomer, manufactured by Toagosei Co., Ltd., AA-6, Mn: 6,000)
-Pigment Blue 15: 3 6.5 parts-Charge control resin 0.7 part (quaternary ammonium salt-containing styrene-acrylic acid resin, "FCA-201-PS"
Fujikura Chemical Co., Ltd.)
・ 20.0 parts of release agent (trade name: HNP-51, melting point: 78 ° C, manufactured by Nippon Seiro)
A mixture consisting of 100.0 parts of toluene was prepared. The mixture was charged into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads having a diameter of 5 mm to obtain a core raw material dispersion.
On the other hand, 5 parts of methyl methacrylate (calculated Tg of the obtained polymer = 105 ° C.), 100 parts of water, and 0.01 part of a charge controlling agent (Bontron E-84, manufactured by Orient Chemical Co., Ltd.) were finely mixed with an ultrasonic emulsifier. By dispersing, an aqueous dispersion of the polymerizable monomer for shell was obtained.
On the other hand, in an aqueous solution in which 9.8 parts of magnesium chloride (water-soluble polyvalent metal salt) was dissolved in 250 parts of ion-exchanged water, 6.9 parts of sodium hydroxide (alkali metal hydroxide) was dissolved in 50 parts of ion-exchanged water. The aqueous solution was gradually added with stirring to prepare a colloidal dispersion of magnesium hydroxide (a colloid of a poorly water-soluble metal hydroxide).
The raw material dispersion for core was added to the magnesium hydroxide colloidal dispersion obtained above, and the mixture was subjected to high shear stirring at 8,000 rpm using a TK homomixer to granulate droplets. The aqueous dispersion containing the granulated monomer mixture was put into a reactor equipped with a stirring blade, and a polymerization reaction was performed at 150 rpm for 10 hours while maintaining the temperature at 70 ° C.
Thereafter, the aqueous dispersion of the polymerizable monomer for shell prepared above and 1 part of a 1% aqueous potassium persulfate solution were added, and the reaction was continued for 5 hours. Then, the reaction was stopped, and a core-shell type structure was obtained. To obtain a toner particle dispersion.
Thereafter, a toner 28 was obtained in the same manner as in the production example of the toner 1.

<Production Example of Toner 29>
[Preparation of toner by emulsion aggregation method]
(Preparation of polymer dispersion)
-300.0 parts of toluene-100.0 parts of polymer A0 The above materials were weighed and mixed, and dissolved at 90 ° C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700.0 parts of ion-exchanged water and dissolved by heating at 90 ° C. Then, the above-mentioned toluene solution and the aqueous solution were mixed, and an ultra-high-speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix). Furthermore, emulsification was performed at a pressure of 200 MPa using a high pressure impact type dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain a polymer dispersion having a polymer particle concentration of 20%.
The 50% particle size (D50) based on the volume distribution of the polymer fine particles was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.
(Preparation of release agent dispersion liquid 1)
・ Release agent (HNP-51, melting point: 78 ° C., manufactured by Nippon Seiwa) 100.0 parts ・ Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5.0 parts ・ Ion-exchanged water 395.0 parts Was weighed and placed in a mixing vessel equipped with a stirrer, heated to 90 ° C., circulated through a CLEARMIX W motion (manufactured by M Technique), and subjected to a dispersion treatment for 60 minutes. The conditions of the distributed processing were as follows.
・ Rotor outer diameter 3cm
・ Clearance 0.3mm
・ Rotor rotation speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the mold is cooled to 40 ° C. under a cooling treatment condition of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 ° C./min. Agent dispersion 1 was obtained.
The 50% particle size (D50) based on the volume distribution of the release agent fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.
(Preparation of Colorant Dispersion 1)
・ Coloring agent 50.0 parts (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ 7.5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) ・ 442.5 parts of ion-exchanged water The above materials are weighed, mixed and dissolved, and a high pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo) is used. The mixture was dispersed for 1 hour to obtain a colorant dispersion 1 having a concentration of 10% of the colorant fine particles 1 in which the colorant was dispersed.
The 50% particle size (D50) based on the volume distribution of the colorant fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.
(Production of Toner 29)
-500.0 parts of polymer dispersion-50.0 parts of release agent dispersion 1-80.0 parts of colorant dispersion 1-160.0 parts of ion-exchange water 160.0 parts of each of the above-mentioned materials are put into a round stainless steel flask. , Mixed. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). A 1.0% aqueous nitric acid solution was added to adjust the pH to 3.0, and then the mixture was stirred at 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. Until heated. The volume average particle size of the formed aggregated particles is appropriately checked using a Coulter Multisizer III, and when the aggregated particles having a size of 6.0 μm are formed, the pH is adjusted to 9.0 with a 5% aqueous sodium hydroxide solution. I made it. Then, it heated to 75 degreeC, continuing stirring. Then, the particles were kept at 75 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the polymer.
Thereafter, the mixture was cooled to 25 ° C., filtered and solid-liquid separated, and then washed with ion-exchanged water. After completion of the washing, the toner particles were dried using a vacuum dryer to obtain toner particles 29 having a weight average particle diameter (D4) of 6.07 μm.
Toner particles 29 were externally added in the same manner as in the production example of toner 1 to obtain toner 29. Table 2 shows the physical properties of Toner 29.

<Production Example of Toner 30>
[Preparation of toner by dissolution suspension method]
(Preparation of fine particle dispersion liquid 1)
683.0 parts of water, 11.0 parts of sodium salt of a methacrylic acid ethylene oxide (EO) adduct sulfuric acid ester (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), and styrene 130 were placed in a reaction vessel equipped with a stirring rod and a thermometer. 0.0 parts, 138.0 parts of methacrylic acid, 184.0 parts of n-butyl acrylate, and 1.0 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain a white suspension. Was. The mixture was heated to a temperature in the system of 75 ° C. and reacted for 5 hours.
Further, 30.0 parts of a 1% aqueous solution of ammonium persulfate was added, and the mixture was aged at 75 ° C. for 5 hours to obtain a fine particle dispersion 1 of a vinyl polymer. The 50% particle size (D50) based on the volume distribution of the fine particle dispersion liquid 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.
(Preparation of Colorant Dispersion 2)
・ C. I. Pigment Blue 15: 3 100.0 parts / ethyl acetate 150.0 parts / glass beads (1 mm) 200.0 parts The above materials are put into a heat-resistant glass container, dispersed with a paint shaker for 5 hours, and then nylon mesh. The glass beads were removed by using to obtain a colorant dispersion 2. The 50% particle size (D50) based on the volume distribution of the colorant dispersion was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.
(Preparation of release agent dispersion liquid 2)
-Release agent (HNP-51, melting point: 78 ° C, manufactured by Nippon Seiro) 20.0 parts-Ethyl acetate: 80.0 parts The above was charged into a sealable reaction vessel, and heated and stirred at 80 ° C. Then, the system was cooled to 25 ° C. over 3 hours while gently stirring the system at 50 rpm to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 30.0 parts of glass beads having a diameter of 1 mm, and dispersed for 3 hours using a paint shaker (manufactured by Toyo Seiki). The glass beads were removed with a nylon mesh. Got. The 50% particle size (D50) based on the volume distribution of the release agent dispersion 2 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.23 μm.
(Preparation of oil phase)
-100.0 parts of polymer A0-85.0 parts of ethyl acetate The above-mentioned material was put into a beaker, and stirred at 3000 rpm for 1 minute using a disper (manufactured by Tokushu Kika Co., Ltd.).
-Release agent dispersion liquid 2 (solid content 20%) 50.0 parts-Colorant dispersion liquid 2 (solid content 40%) 12.5 parts-Ethyl acetate 5.0 parts The mixture was stirred at 6000 rpm for 3 minutes using a specialty chemical company to prepare an oil phase.
(Preparation of aqueous phase)
・ 15.0 parts of fine particle dispersion liquid ・ 30.0 parts of aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON7, manufactured by Sanyo Chemical Industry Co., Ltd.) ・ 955.0 parts of ion-exchanged water The mixture was stirred at 3000 rpm for 3 minutes to prepare an aqueous phase.
(Manufacture of Toner 30)
The oil phase was put into the water phase, and dispersed by a TK homomixer (manufactured by Tokushu Kika) at 10,000 rpm for 10 minutes. Thereafter, the solvent was removed at 30 ° C. under a reduced pressure of 50 mmHg for 30 minutes. Next, filtration was performed, and the operation of filtering and redispersing in ion-exchanged water was repeated until the conductivity of the slurry became 100 μS, thereby removing the surfactant and obtaining a filter cake.
After the filter cake was vacuum dried, toner particles 30 were obtained by performing air classification.
Toner particles 30 were externally added in the same manner as in the production example of toner 1 to obtain toner 30. Table 2 shows the physical properties of Toner 30.

<Production Example of Toner 31>
[Production of toner by pulverization method]
-100.0 parts of polymer A0-C.I. I. Pigment Blue 15: 3 6.5 parts ・ Release agent (HNP-51, melting point 78 ° C., manufactured by Nippon Seiro) 2.0 parts ・ Charge control agent 1.5 parts (quaternary ammonium salt, Orient Chemical Co., Ltd.) "BONTRON (registered trademark) P-51"
After the above materials were premixed with an FM mixer (manufactured by Nippon Coke Industry Co., Ltd.), they were melt-kneaded by a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.).
The obtained kneaded material was cooled, coarsely crushed by a hammer mill, and then crushed by a mechanical crusher (T-250 manufactured by Turbo Kogyo Co., Ltd.). The particles were classified using a split classifier to obtain toner particles 31 having a weight average particle diameter (D4) of 7.0 μm.
Toner particles 31 were externally added in the same manner as in the production example of toner 1 to obtain toner 31. Table 2 shows the physical properties of Toner 31.

<Production Example of Toner 32>
With respect to 100.0 parts of toner particles 31 produced in the production example of toner 31,
0.7 parts of silica fine particles 1 (silica fine particles having a number-average particle diameter of primary particles of 10 nm of primary particles hydrophobized with amino-modified silicone oil),
1.0 part of silica fine particles 2 (silica fine particles having a number average primary particle diameter of 55 nm which has been subjected to a hydrophobic treatment with an amino-modified silicone oil), and
0.5 parts of conductive titanium oxide particles (“EC-100” manufactured by Titanium Industry Co., Ltd., substrate: TiO ₂ particles, coating layer: Sb-doped SnO ₂ film, number average particle diameter of primary particles: 0.35 μm) ,
Dry mixing was performed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes to obtain toner 32. Table 2 shows the physical properties of the obtained toner 32.

<Production Example of Toner 33>
[Production of toner by pulverization method]
-100.0 parts of polymer A0-C.I. I. Pigment Blue 15: 3 6.5 parts ・ Release agent (HNP-51, melting point 78 ° C., manufactured by Nippon Seiro) 2.0 parts ・ Charge control agent 1.5 parts (quaternary ammonium salt, Orient Chemical Co., Ltd.) "BONTRON (registered trademark) P-51"
After the above materials were premixed with an FM mixer (manufactured by Nippon Coke Industry Co., Ltd.), they were melt-kneaded by a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.).
The obtained kneaded material was cooled, coarsely crushed by a hammer mill, and then crushed by a mechanical crusher (T-250 manufactured by Turbo Kogyo Co., Ltd.). Classification was performed using a split classifier to obtain toner core particles having a weight average particle diameter (D4) of 7.0 μm.
On the other hand, 300 mL of ion-exchanged water was put into a three-neck flask having a capacity of 1 L equipped with a thermometer and stirring blades, and the temperature inside the flask was kept at 30 ° C. using a water bath. Then, the pH of the aqueous medium in the flask was adjusted to 4 by adding diluted hydrochloric acid to the flask. After the pH adjustment, 2 mL of an aqueous solution of a hexamethylolmelamine prepolymer (“Milven (registered trademark) Resin SM-607, manufactured by Showa Denko KK, solid content concentration: 80% by mass)” was added as a raw material for the shell layer to the flask. did. Next, the contents of the flask were stirred, and the raw material for the shell layer was dissolved in an aqueous medium to obtain an aqueous solution of the raw material for the shell layer.
300 g of the toner core particles were added to the three-necked flask containing the aqueous solution, and the contents of the flask were stirred at a speed of 200 rpm for 1 hour. Next, 300 mL of ion-exchanged water was added, and the temperature inside the flask was raised to 70 ° C. at a rate of 1 ° C./min while stirring at 100 rpm. After the temperature was raised, the contents of the flask were continuously stirred at 70 ° C. and 100 rpm for 2 hours. Thereafter, the pH of the contents of the flask was adjusted to 7 by adding sodium hydroxide. Next, the content of the flask was cooled to room temperature to obtain a dispersion containing toner base particles.
Using a Buchner funnel, wet cake-like toner base particles were filtered from the dispersion containing the toner base particles. The toner base particles in the form of a wet cake were dispersed in ion-exchanged water to wash the toner base particles. Next, the toner base particles were dried by hot air drying to obtain toner particles 33. The toner particles 33 were externally added in the same manner as in the production example of the toner 1 to obtain a toner 33. Table 2 shows the physical properties of Toner 33.

<Production Examples of Toners 34 to 36>
(Preparation of amorphous resin dispersion)
-Toluene 300.0 parts-Amorphous resin 100.0 parts The above materials were weighed and mixed, and dissolved at 90 ° C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700.0 parts of ion-exchanged water, and dissolved by heating at 90 ° C.
Then, the toluene solution and the aqueous solution were mixed, and the mixture was mixed with an ultrahigh-speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix).
Furthermore, emulsification was performed at a pressure of 200 MPa using a high pressure impact type dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an amorphous resin dispersion having a concentration of amorphous resin fine particles of 20%.
The 50% particle size (D50) based on the volume distribution of the amorphous resin fine particles was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.38 μm.
(Production of Toners 34 to 36)
Toner particles 34 to 36 were obtained in the same manner as in Production Example of Toner 29 except that the amount of the dispersion used was changed as shown in Table 4.
Further, toner particles 34 to 36 were subjected to the same external addition as in the production example of toner 29, whereby toners 34 to 36 were obtained. Table 2 shows the physical properties of Toners 34 to 36.

<Production Examples of Toners 37 to 43>
In the production example of the toner 1, the types and amounts of the polymerizable monomer, the macromonomer, and the charge control agent or the charge control resin to be used are changed in the same manner except that the toner particles 37 to 37 are changed as shown in Table 1. 43 was obtained.
Further, toners 37 to 43 were obtained by externally adding the toner particles 37 to 43 in the same manner as in the production example of the toner 1. Table 2 shows the physical properties of Toners 37 to 43.

<Example 1>
The following evaluation was performed on Toner 1.
<1> Evaluation of low-temperature fixability A 10 mm × 10 mm square image was printed using a non-magnetic one-component development type printer equipped with a commercially available positively charged toner modified so that it operates even when the fixing unit was removed. Output an unfixed image of an image pattern in which 9 points are evenly arranged on the entire transfer paper.
The transfer paper used was a Fox River Bond (90 g / m ² ), and the amount of toner on the transfer paper was 0.80 mg / cm ² . The toner was allowed to stand in a normal temperature and normal humidity (N / N) environment (23 ° C., 60% RH) for 48 hours before passing the paper.
As the fixing device, an external fixing device in which the fixing device of LBP-7700C was detached and operated outside the laser beam printer was used.
The external fixing unit raised the fixing temperature from 100 ° C. in steps of 10 ° C., and passed the unfixed image under the condition of process speed: 240 mm / sec.
The fixed image that passed through the external fixing device was rubbed with a Silbon paper [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd.)] under a load of 50 g / cm ² . The temperature at which the density reduction rate before and after rubbing became 20% or less was defined as the fixing start temperature, and the low-temperature fixability was evaluated according to the following criteria. Table 5 shows the evaluation results.
[Evaluation criteria]
A: Fixing start temperature is 100 ° C
B: Fixing start temperature is 110 ° C
C: Fixing start temperature is 120 ° C.
D: Fixing start temperature is 130 ° C

<2> Evaluation of heat-resistant storage stability Evaluation of the heat-resistant storage stability was performed to evaluate the stability during storage.
6 g of the toner 1 is placed in a 100 mL polypropylene cup, and the temperature is 50 ° C.
%, The toner was allowed to stand for 10 days, and then the degree of aggregation of the toner was measured as follows, and evaluated according to the following criteria.
As a measuring device, a device in which a digital display type vibrometer "Digi Vibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side of the shaking table of "Powder Tester" (manufactured by Hosokawa Micron Corporation) was used.
Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were set in this order on a vibration table of the powder tester from below. The measurement was performed as follows in a 23 ° C., 60% RH environment.
(1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display type vibrometer was 0.60 mm (peak-to-peak).
(2) The toner left for 10 days as described above was left in advance in an environment of 23 ° C. and 60% RH for 24 hours, and 5 g of the toner was precisely weighed and gently placed on a 150 μm sieve at the uppermost stage. Was.
(3) After the sieve was vibrated for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation. Table 5 shows the evaluation results.
Cohesion degree (%) = {(mass of sample on sieve with mesh size of 150 μm (g)) / 5 (g)} × 100
+ {(Sample mass (g) on sieve with mesh size of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Mass of sample (g) on sieve with mesh size of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: Aggregation degree is less than 20% B: Aggregation degree is 20% or more and less than 25% C: Aggregation degree is 25% or more and less than 30% D: Aggregation degree is 30% or more

<3> Evaluation of Chargeability (Fog) The chargeability of the toner was evaluated by fog.
After filling the toner 1 obtained above into a commercially available non-magnetic one-component developing system printer (manufactured by Brother Industries, Ltd., trade name: MFC-9840-CDW), the printing paper is set,
It was left for 3 days in a normal temperature and normal humidity (N / N) environment (23 ° C., 60% RH) and a high temperature and high humidity (H / H) environment (32.5 ° C., 80% RH). After the standing, one image having a white background was printed out under each environment. The reflectance of the obtained image was measured using a reflection densitometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.). A green filter was used as a filter used in the measurement. The worst value Ds (%) of the reflectance of the white background portion and Dr-Ds when the reflectance of the transfer material before image formation was assumed to be Dr (%) were evaluated as fog, and the evaluation was made according to the following criteria. Table 5 shows the evaluation results.
A: Fog is less than 1.0% B: Fog is 1.0% or more and less than 3.0% C: Fog is 3.0% or more and less than 5.0% D: Fog is 5.0% or more

<4> Evaluation of Durability A commercially available non-magnetic one-component developing system printer (manufactured by Brother Industries, Ltd., trade name: MFC-9840-CDW) was charged with the toner 1 obtained above, and then printing paper was set. .
An image having a printing rate of 1% was continuously output under an environment of 23 ° C. and 60% RH.
Every time 1,000 sheets were output, a solid image and a halftone image were output, and the presence or absence of vertical streaks caused by fusion of the toner to the regulating member, so-called development streaks, was visually checked.
Finally, 20,000 images were output. Table 5 shows the evaluation results.
[Evaluation criteria]
A: No occurrence even at 20,000 sheets B: More than 19,000 sheets and less than 20,000 sheets C: More than 17,000 sheets and less than 19,000 sheets D: Occurs at less than 17,000 sheets

<Examples 2 to 36>
The same evaluation as in Example 1 was performed on the toners 2 to 36. Table 5 shows the results.

<Examples 37 to 39>
With respect to the toners 31 to 33, the following evaluations were also performed in addition to the above evaluations shown in Example 1.
After filling the toners 31 to 33 obtained above into a commercially available multifunction device (Kyocera Document Solutions Inc., trade name: TASKalfa 250ci), a printing paper was set.
After having been left for 3 days in a normal temperature and normal humidity (N / N) environment (23 ° C., 60% RH) and a low temperature and low humidity (L / L) environment (15 ° C., 10% RH), an image having a white background under each environment Was printed out.
The reflectance of the obtained image was measured using a reflection densitometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.). A green filter was used as a filter used in the measurement. The worst value Ds (%) of the reflectance of the white background portion and Dr-Ds when the reflectance of the transfer material before image formation was assumed to be Dr (%) were evaluated as fog, and the evaluation was made according to the following criteria. Table 6 shows the evaluation results.
A: Fog is less than 1.0% B: Fog is 1.0% or more and less than 3.0% C: Fog is 3.0% or more and less than 5.0% D: Fog is 5.0% or more

<Comparative Examples 1 to 7>
The same evaluation as in Example 1 was performed on the toners 37 to 43. Table 5 shows the results.

Hereinafter, the abbreviations in the table are as follows.
BEA: behenyl acrylate BEMA: behenyl methacrylate SA: stearyl acrylate MYA: myristyl acrylate OA: octacosa acrylate HA: hexadecyl acrylate MN: methacrylonitrile AN: acrylonitrile HPMA: 2-hydroxypropyl methacrylate AM: acrylamide UT: Urethane group-containing monomer UR: Urea group-containing monomer AA: Acrylic acid VA: Vinyl acetate MA: Methyl acrylate St: Styrene MM: Methyl methacrylate AA-6: Macromonomer "AA-6" Toa Gosei AK-32 manufactured by Co., Ltd .: Macromonomer “AK-32” manufactured by Toagosei Co., Ltd. In the charge control agent / resin in Table 1,
“1” represents “FCA-201-PS” manufactured by Fujikura Kasei Co., Ltd.
"2" represents "BONTRON (registered trademark) P-51" manufactured by Orient Chemical Industry Co., Ltd.

表２中のＸは、結着樹脂中の重合体Ａの含有量（質量％）を表す。

X in Table 2 represents the content (% by mass) of the polymer A in the binder resin.

  10: cell, 10a: recess for accommodating sample

Claims (15)

A positively chargeable toner having toner particles containing a binder resin,
The binder resin is
A first monomer unit derived from a first polymerizable monomer, and
Containing a polymer A having a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol%, based on the total number of moles of all monomer units in the polymer A;
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol%, based on the total number of moles of all monomer units in the polymer A;
When the SP value of the first monomer unit is SP ₁₁ (J / cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J / cm ³ ) ^0.5 , the following formula is used. Satisfies (1),
A positively chargeable toner, wherein the work function of the toner is from 5.0 eV to 5.4 eV.
3.00 ≦ (SP ₂₁ −SP ₁₁ ) ≦ 25.00 (1) A positively chargeable toner having toner particles containing a binder resin,
The binder resin is
A first polymerizable monomer, and
Containing polymer A which is a polymer of a composition containing a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Satisfies the following expression (2),
A positively chargeable toner, wherein the work function of the toner is from 5.0 eV to 5.4 eV.
0.60 ≦ (SP ₂₂ −SP ₁₂ ) ≦ 15.00 (2)   The content ratio of the second monomer unit in the polymer A is from 40.0 mol% to 95.0 mol% based on the total number of moles of all monomer units in the polymer A. 4. The positively chargeable toner according to item 1.   The content ratio of the second polymerizable monomer in the composition is 40.0 mol% to 95.0 mol%, based on the total number of moles of all the polymerizable monomers in the composition. The positively chargeable toner according to claim 2.   The positively chargeable toner according to any one of claims 1 to 4, wherein the content of the polymer A in the binder resin is 50.0% by mass or more. The method according to claim 1, wherein the first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms. A positively chargeable toner according to any one of the preceding claims. The positively chargeable toner according to any one of claims 1 to 6, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is a nitrile group (—C≡N),
An amide group (—C (＝ O) NHR ¹⁰ (where R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms));
Hydroxy group,
—COOR ¹¹ (where R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
Urethane group (-NHCOOR ¹² (where R ¹² is an alkyl group having 1 to 4 carbon atoms)),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ , wherein R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
And R ³ is a hydrogen atom or a methyl group. )
(In the formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The positively chargeable toner according to any one of claims 1 to 7, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is a nitrile group (—C≡N),
An amide group (—C (＝ O) NHR ¹⁰ (where R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms));
Hydroxy group,
—COOR ¹¹ (where R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ (where R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)),
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
And R ³ is a hydrogen atom or a methyl group. )
(In the formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The polymer A has a third monomer unit derived from a third polymerizable monomer different from the first polymerizable monomer and the second polymerizable monomer,
The positively chargeable toner according to any one of claims 1 to 8, wherein the third polymerizable monomer is at least one selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate.   The positive charge toner according to any one of claims 1 to 9, wherein the toner contains at least one selected from the group consisting of a positive charge control agent and a positive charge control resin.   The positively chargeable toner according to any one of claims 1 to 10, wherein the polymer A is a vinyl polymer. The polymer A further comprises:
Contains monomer units derived from macromonomers,
The number average molecular weight of the macromonomer is 1,000 to 20,000,
The macromonomer has an acryloyl group or a methacryloyl group at a molecular chain terminal,
The content ratio of the monomer unit derived from the macromonomer in the polymer A is from 1.0 × 10 ⁻⁴ mol% to 3.0 ×, based on the total number of moles of all the monomer units in the polymer A. The positively chargeable toner according to claim 1, wherein the content is 10 ^-1 mol%.   The positively chargeable toner according to claim 12, wherein the macromonomer is at least one selected from the group consisting of a (meth) acrylate polymer having an acryloyl group or a methacryloyl group at a molecular terminal.   The positively chargeable toner according to claim 1, wherein the toner contains an external additive, and has a conductive layer on a surface of the external additive. The positively chargeable toner according to claim 14, wherein the conductive layer is a film forming body containing tin oxide doped with antimony.

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